Compound, core-shell dye, photosensitive resin composition including the same, and color filter

ABSTRACT

A compound represented by specific chemical formula, a core including the same, and core-shell dye including a shell surrounding the core, a photosensitive resin composition including the same, and a color filter manufactured using the photosensitive resin composition are disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This is the U.S. national phase application based on PCT Application No.PCT/KR2017/006197, filed Jun. 14, 2017, which is based on Korean PatentApplication No. 10-2016-0125111, filed Sep. 28, 2016, the entirecontents of all of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION (a) Field of the Invention

This disclosure relates to a novel compound, a core-shell dye, aphotosensitive resin composition including the same, and a color filtermanufactured using the same.

(b) Description of the Related Art

A liquid crystal display device among many kinds of displays has anadvantage of lightness, thinness, low cost, low power consumption foroperation, and improved adherence to an integrated circuit and has beenmore widely used for a laptop computer, a monitor, and a TV screen.

The liquid crystal display device includes a lower substrate on which ablack matrix, a color filter, and an ITO pixel electrode are formed, andan upper substrate on which an active circuit portion including a liquidcrystal layer, a thin film transistor, and a capacitor layer and an ITOpixel electrode are formed.

Color filters are formed in a pixel region by sequentially stacking aplurality of color filters (in general, formed of three primary colorssuch as red (R), green (G), and blue (B) in a predetermined order toform each pixel, and a black matrix layer is disposed in a predeterminedpattern on a transparent substrate to form a boundary between thepixels.

The pigment dispersion method that is one of methods of forming a colorfilter provides a colored thin film by repeating a series of processessuch as coating a photopolymerizable composition including a colorant ona transparent substrate including a black matrix, exposing a formedpattern to light, removing a non-exposed part with a solvent, andthermally curing the same.

A coloring photosensitive resin composition used for manufacturing acolor filter according to the pigment dispersion method generallyincludes an alkali-soluble resin, a photopolymerizable monomer, aphotopolymerization initiator, an epoxy resin, a solvent, otheradditives, and the like. The pigment dispersion method is activelyapplied to manufacture an LCD of a mobile phone, a laptop, a monitor,and TV.

However, a photosensitive resin composition for a color filter for thepigment dispersion method has recently required improved performance aswell as excellent pattern characteristics. Particularly, high colorreproducibility and high luminance and high contrast ratiocharacteristics are urgently required. An image sensor is a part forphotographing images in a portable phone camera or DSC (a digital stillcamera).

It may be classified as a charge-coupled device (CCD) image sensor and acomplementary metal oxide semiconductor (CMOS) image sensor dependingupon the manufacturing process and the application method.

A color imaging device for a charge-coupled device image sensor or acomplementary metal oxide semiconductor image sensor includes colorfilters each having filter segments of mixing primary color of red,green, and blue, and the colors are separated. A recent color filtermounted in the color imaging device has a pattern size of 2 μm or less,which is 1/100th to 1/200th of the pattern size of a conventional colorfilter pattern for LCDs.

Accordingly, increased resolution and decreased pattern residues areimportant factors for determining the performance of a device. A colorfilter manufactured by using a conventional pigment-type photosensitiveresin composition has a limit in luminance and a contrast ratio due tothe size of pigment particles.

In addition, a color imaging device for an image sensor needs a smallerdispersion particle diameter for forming a fine pattern. In order tocorrespond to the requirements, an attempt to realize a color filterhaving improved luminance and a contrast ratio has been made byintroducing a dye forming no particle instead of the pigment to preparea photosensitive resin composition appropriate for the dye.

However, a dye has inferior durability such as light resistance and heatresistance, and the like to a pigment and thus luminance may bedeteriorated.

SUMMARY OF THE INVENTION

An embodiment provides a novel compound having improved luminance andcontrast ratio.

Another embodiment provides a core-shell dye including the novelcompound.

Yet another embodiment provides a photosensitive resin compositionincluding the novel compound or the core-shell dye.

Still another embodiment provides a color filter manufactured using thephotosensitive resin composition.

An embodiment provides a compound represented by Chemical Formula 1.

In Chemical Formula 1,

R¹ is represented by Chemical Formula 2, and

R² is a substituted C6 to C20 aryl group,

wherein, in Chemical Formula 2,

R³ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkylgroup,

R⁴ is a substituted or unsubstituted C1 to C10 alkyl group, and

n is an integer ranging from 0 to 5.

The n may be an integer of 1 or 2.

R² may be represented by Chemical Formula 3.

In Chemical Formula 3,

R⁵ and R⁶ are independently C1 to C7 alkyl group.

The compound represented by Chemical Formula 1 may be represented by oneselected from compounds represented by Chemical Formula 1-1 to ChemicalFormula 1-7.

Another embodiment provides a core-shell dye including a core includingthe compound represented by Chemical Formula 1; and a shell surroundingthe core.

The shell may be represented by Chemical Formula 4 or Chemical Formula5.

In Chemical Formula 4 and Chemical Formula 5,

L^(a) to L^(d) are independently a single bond or a substituted orunsubstituted C1 to C10 alkylene group.

L^(a) to L^(d) may independently be a substituted or unsubstituted C1 toC10 alkylene group.

The shell may be represented by Chemical Formula 4-1 or Chemical Formula5-1.

A cage width of the shell may range from 6.5 Å to 7.5 Å.

The core may have a length of 1 nm to 3 nm.

The core may have a maximum absorption peak in a wavelength of 530 nm to680 nm.

The core-shell dye may be selected from compounds represented byChemical Formula 6 to Chemical Formula 19.

The core-shell dye may include the core and the shell in a mole ratio of1:1.

The core-shell dye may be a green dye.

Another embodiment provides a photosensitive resin composition includingthe compound or the core-shell dye.

The photosensitive resin composition may further include a binder resin,a photopolymerizable monomer, a photopolymerization initiator, and asolvent.

The photosensitive resin composition may further include a pigment.

The photosensitive resin composition may include 0.5 wt % to 10 wt % ofthe compound or the core-shell dye; 0.1 wt % to 30 wt % of the binderresin; 0.1 wt % to 30 wt % of the photopolymerizable monomer; 0.1 wt %to 5 wt % of the photopolymerization initiator; and a balance amount ofthe solvent based on a total amount of the photosensitive resincomposition.

The photosensitive resin composition may further include malonic acid,3-amino-1,2-propanediol, a silane-based coupling agent including a vinylgroup or a (meth)acryloxy group, a leveling agent, a surfactant, aradical polymerization initiator, or a combination thereof.

Another embodiment provides a color filter manufactured using thephotosensitive resin composition.

Other embodiments of the present invention are included in the followingdetailed description.

The compound or the core-shell dye according to an embodiment realizes acolor filter having improved luminance and contrast ratio.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a view showing a cage width of a shell represented by ChemicalFormula 5-1.

DETAILED DESCRIPTION

Hereinafter, embodiments of the present invention are described indetail. However, these embodiments are exemplary, the present inventionis not limited thereto and the present invention is defined by the scopeof claims.

In the present specification, when specific definition is not otherwiseprovided, “substituted” refers to replacement of at least one hydrogenatom of a compound by a substituent of a halogen atom (F, Cl, Br, or I),a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group,an amine group, an imino group, an azido group, an amidino group, ahydrazino group, a hydrazono group, a carbonyl group, a carbamyl group,a thiol group, an ester group, an ether group, a carboxyl group or asalt thereof, a sulfonic acid group or a salt thereof, a phosphoric acidor a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, aC2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkylgroup, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, aC2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group,a C2 to C20 heterocycloalkynyl group, or a combination thereof.

In the present specification, when specific definition is not otherwiseprovided, a “heterocycloalkyl group”, a “heterocycloalkenyl group”, a“heterocycloalkynyl group,” and a “heterocycloalkylene group” refer toeach cyclic compound of cycloalkyl, cycloalkenyl, cycloalkynyl, andcycloalkylene including at least one heteroatom of N, O, S, or P.

In the present specification, when specific definition is not otherwiseprovided, “(meth)acrylate” refers to both “acrylate” and “methacrylate”.

In the present specification, when specific definition is not otherwiseprovided, the term “combination” refers to mixing or copolymerization.

In the present specification, when a definition is not otherwiseprovided, in a chemical formula, hydrogen is bonded at the position whena chemical bond is not drawn where supposed to be given.

In the present specification, when specific definition is not otherwiseprovided, “*” indicates a point where the same or different atom orchemical formula is linked.

A compound according to an embodiment is represented by Chemical Formula1.

In Chemical Formula 1,

R¹ is represented by Chemical Formula 2, and

R² is a substituted C6 to C20 aryl group,

wherein, in Chemical Formula 2,

R³ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkylgroup,

R⁴ is a substituted or unsubstituted C1 to C10 alkyl group, and

n is an integer ranging from 0 to 5.

R¹ and R² may not be linked to form a fused ring.

The compound represented by Chemical Formula 1 has excellent greenspectral characteristics and a high molar extinction coefficient and maybe used as a green dye. However, the compound has insufficientdurability compared with a pigment and thus may deteriorate luminanceduring a baking process after formed into a color resist. A compoundaccording to an embodiment includes a benzyl group (represented byChemical Formula 2) and a substituted aryl functional group (morespecifically represented by Chemical Formula 3) which are differentsubstituents and are symmetrical to each other, and thereby durabilitymay be improved and a color filter having high luminance and a highcontrast ratio may be realized.

For example, the n may be an integer of 1 or 2.

For example, R² may be represented by Chemical Formula 3.

In Chemical Formula 3,

R⁵ and R⁶ are independently C1 to C7 alkyl group.

When the compound represented by Chemical Formula 1 is used in aphotosensitive resin composition (e.g., as a dye), solubility in apost-described solvent may be greater than or equal to 5, for example,range from 5 to 10. The solubility may be obtained by an amount (g) ofthe dye (compound) dissolved in 100 g of the solvent. When the compound(e.g., dye) has solubility within the range, compatibility and coloringproperties with other components in the photosensitive resincomposition, that is, post-described binder resin, photopolymerizablemonomer, and photopolymerization initiator may be secured, andprecipitation of the dye may be prevented.

The compound represented by Chemical Formula 1 may have excellent heatresistance. That is, a thermal decomposition temperature measured usinga thermogravimetric analyzer (TGA) may greater than or equal to 200° C.,for example, 200° C. to 300° C.

The compound represented by Chemical Formula 1 has three kinds ofresonance structures as shown in the following diagram, but in thepresent specification, the compound having one kind of a resonancestructure and represented by Chemical Formula 1 is shown forconvenience. In other words, the compound represented by ChemicalFormula 1 may have any one structure of the three resonance structures.

The compound represented by Chemical Formula 1 may be selected fromcompounds represented by Chemical Formula 1-1 to Chemical Formula 1-7.

A core-shell dye according to another embodiment has a structureconsisting of a core and a shell surrounding the core. The core includesthe compound represented by Chemical Formula 1. Specifically, the shellmay be a huge cyclic compound and the shell surrounds the compoundrepresented by Chemical Formula 1 to form a coating layer.

In an embodiment, the compound represented by Chemical Formula 1 issurrounded by the shell corresponding to a huge cyclic compound, thatis, the compound represented by Chemical Formula 1 is present inside thehuge cycle, and thereby durability of the core-shell dye may be improvedand a color filter having high luminance and a high contrast ratio maybe realized.

A length of the compound represented by Chemical Formula 1 included inthe core or composed of the core may be 1 nm to 3 nm, for example, 1.5nm to 2 nm. When the compound represented by Chemical Formula 1 has alength within the range, a core-shell dye may easily have a structurethat a shell surrounds a core. In other words, the compound representedby Chemical Formula 1 has a length within the range and thus may have astructure that the huge cyclic compound, that is, the shell surroundsthe compound represented by Chemical Formula 1. When a compound having alength out of the range is used, the structure that the shell does notsurround the core compound may not be obtained, and durability may notbe improved.

The compound represented by Chemical Formula 1 included in the core orcomposed of the core may have a maximum absorption peak in a wavelengthof 530 nm to 680 nm. The core-shell dye using the compound representedby Chemical Formula 1 having the spectral characteristics as a core isfor example used as a green dye and thereby a photosensitive resincomposition for a color filter having high luminance and high contrastratio may be provided.

The shell surrounding the core including the compound represented byChemical Formula 1 may be represented by Chemical Formula 4 or ChemicalFormula 5.

In Chemical Formula 4 and Chemical Formula 5,

L^(a) to L^(d) are independently a single bond or a substituted orunsubstituted C1 to C10 alkylene group.

In Chemical Formula 4 or Chemical Formula 5, L^(a) to L^(d) mayindependently be a substituted or unsubstituted C1 to C10 alkylenegroup. In this case, a structure having improved solubility where ashell surrounds the core including the compound represented by ChemicalFormula 1 is easily formed.

For example, the core-shell dye according to an embodiment includes anon-covalent bond, that is, a hydrogen bond between an oxygen atom ofthe compound represented by Chemical Formula 1 and a nitrogen atom ofthe shell represented by Chemical Formula 4 or Chemical Formula 5.

The shell may be for example represented by Chemical Formula 4-1 orChemical Formula 5-1.

A cage width of the shell may range from 6.5 Å to 7.5 Å and a volume ofthe shell may range from 10 Å to 16 Å. The cage width in this disclosurerefers to an internal distance of the shell, for example in a shellrepresented by Chemical Formula 4-1 or Chemical Formula 5-1, a distancebetween two different phenylene groups in which both methylene groupsare linked (See FIG. 1). When the shell has a cage width within therange, a core-shell dye having a structure surrounding the coreincluding the compound represented by Chemical Formula 1 may beobtained, and thus a color filter having improved durability and highluminance may be realized when the core-shell dye is added to aphotosensitive resin composition.

The core-shell dye includes the core including the compound representedby Chemical Formula 1 and the shell in a mole ratio of 1:1. When thecore and shell are present within the mole ratio, a coating layer(shell) surrounding the core including the compound represented byChemical Formula 1 may be formed well.

For example, the core-shell dye may be selected from compoundsrepresented by Chemical Formula 6 to Chemical Formula 19, but is notlimited thereto.

The core-shell dye may be used alone as a green dye and may be mixedwith an auxiliary dye.

The auxiliary dye may be a triarylmethane-based dye, ananthraquinone-based dye, a benzylidene-based dye, a cyanine-based dye,phthalocyanine-based dye, an azaporphyrin-based dye, an indigo-baseddye, a xanthene-based dye, an azo-based dye, and the like.

The core-shell dye may be mixed with a pigment.

The pigment may be a red pigment, a green pigment, a blue pigment, ayellow pigment, a black pigment, and the like.

Examples of the red pigment may be C.I. red pigment 254, C.I. redpigment 255, C.I. red pigment 264, C.I. red pigment 270, C.I. redpigment 272, C.I. red pigment 177, C.I. red pigment 89, and the like.Examples of the green pigment may be C.I. green pigment 36, C.I. greenpigment 7, C.I. green pigment 58 C.I. green pigment 59, C.I. greenpigment 62, and the like. Examples of the blue pigment may be a copperphthalocyanine pigment such as C.I. blue pigment 15:6, C.I. blue pigment15, C.I. blue pigment 15:1, C.I. blue pigment 15:2, C.I. blue pigment15:3, C.I. blue pigment 15:4, C.I. blue pigment 15:5, C.I. blue pigment16, and the like. Examples of the yellow pigment may be anisoindoline-based pigment such as C.I. yellow pigment 139, and the like,a quinophthalone-based pigment such as C.I. yellow pigment 138, and thelike; a nickel complex pigment such as C.I. yellow pigment 150, and thelike. Examples of the black pigment may be aniline black, peryleneblack, titanium black, carbon black, and the like. The pigment may beused alone or as a mixture of two or more and is not limited thereto.

The pigment may be included in the photosensitive resin composition fora color filter in a pigment dispersion liquid state. The pigmentdispersion liquid may consist of the pigment and a solvent, a dispersingagent, a dispersing resin, and the like.

The solvent may be ethylene glycol acetate, ethyl cellosolve, propyleneglycol methyl ether acetate, ethyl lactate, polyethylene glycol,cyclohexanone, propylene glycol methyl ether, and the like, andpreferably propylene glycol methyl ether acetate.

The dispersing agent helps uniform dispersion of the pigment, and mayinclude a non-ionic, anionic, or cationic dispersing agent. Specificexamples may be polyalkylene glycol or esters thereof, polyoxy alkylene,polyhydric alcohol ester alkylene oxide addition products, alcoholalkylene oxide addition products, sulfonate esters, sulfonate salts,carboxylate esters, carboxylate salts, alkyl amide alkylene oxideaddition products, alkyl amines, and may be used alone or as a mixtureof two or more.

The dispersing resin may be an acryl-based resin including a carboxylgroup, and improves stability of the pigment dispersion liquid andpattern properties of a pixel.

When the core-shell dye and the pigment are mixed, the core-shell dyeand the pigment may be mixed in a weight ratio of 1:9 to 9:1 andspecifically in a weight ratio of 3:7 to 7:3. When they are mixed withinthe weight ratio range, high luminance and contrast ratios may beobtained while color characteristics are maintained.

According to another embodiment, a photosensitive resin compositionincluding the compound represented by Chemical Formula 1 or thecore-shell dye is provided.

The photosensitive resin composition includes (A) a colorant (thecompound represented by Chemical Formula 1 or the core-shell dye), (B) abinder resin, (C) a photopolymerizable monomer, (D) aphotopolymerization initiator, and (E) a solvent.

Hereinafter, each component is specifically described.

(A) Colorant

The colorant may include the compound represented by Chemical Formula 1and/or the core-shell dye and the compound represented by ChemicalFormula 1 and/or the core-shell dye are described above.

The colorant may further include a pigment in addition to the compoundrepresented by Chemical Formula 1 and/or the core-shell dye and thepigment is described above.

The compound represented by Chemical Formula 1 and/or the core-shell dyemay be included in an amount of 0.5 wt % to 10 wt %, for example 0.5 wt% to 5 wt % based on a total amount of the photosensitive resincomposition for a color filter. When the compound represented byChemical Formula 1 and/or the core-shell dye is used within the range,high luminance and a high contrast ratio at a desirable color coordinatemay be realized.

(B) Binder Resin

The binder resin is a copolymer of a first ethylenic unsaturated monomerand a second ethylenic unsaturated monomer that is copolymerizabletherewith, and is resin including at least one acryl-based repeatingunit.

The first ethylenic unsaturated monomer is an ethylenic unsaturatedmonomer including at least one carboxyl group. Examples of the monomerinclude (meth)acrylic acid, maleic acid, itaconic acid, fumaric acid, ora combination thereof.

The first ethylenic unsaturated monomer may be included in an amount of5 wt % to 50 wt %, for example 10 wt % to 40 wt % based on a totalamount of the alkali soluble resin.

The second ethylenic unsaturated monomer may be an aromatic vinylcompound such as styrene, α-methylstyrene, vinyl toluene, vinylbenzylmethyl ether and the like; an unsaturated carboxylate ester compoundsuch as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate,2-hydroxyethyl(meth)acrylate, 2-hydroxy butyl(meth)acrylate,benzyl(meth)acrylate, cyclohexyl(meth)acrylate, phenyl(meth)acrylate,and the like; an unsaturated amino alkyl carboxylate ester compound suchas 2-aminoethyl(meth)acrylate, 2-dimethylaminoethyl(meth)acrylate, andthe like; a carboxylic acid vinyl ester compound such as vinyl acetate,vinyl benzoate, and the like; an unsaturated glycidyl carboxylate estercompound such as glycidyl(meth)acrylate, and the like; a vinyl cyanidecompound such as (meth)acrylonitrile and the like; an unsaturated amidecompound such as (meth)acrylamide, and the like; and the like, and maybe used alone or as a mixture of two or more.

Specific examples of the binder resin may be a methacrylicacid/benzylmethacrylate copolymer, a methacrylicacid/benzylmethacrylate/styrene copolymer, a methacrylicacid/benzylmethacrylate/2-hydroxyethylmethacrylate copolymer, amethacrylic acid/benzylmethacrylate/styrene/2-hydroxyethylmethacrylatecopolymer and the like, but are not limited thereto. These may be usedalone or as a mixture of two or more.

A weight average molecular weight of the binder resin may be 3,000 g/molto 150,000 g/mol, for example 5,000 g/mol to 50,000 g/mol, for example20,000 g/mol to 30,000 g/mol. When the binder resin has a weight averagemolecular weight within the range, close contacting properties with asubstrate and physicochemical properties are improved and viscosity isappropriate.

An acid value of the binder resin may be 15 mgKOH/g to 60 mgKOH/g, forexample 20 mgKOH/g to 50 mgKOH/g. When the binder resin has an acidvalue within the range, excellent resolution of a pixel may be obtained.

The binder resin may be included in an amount of 0.1 wt % to 30 wt %,for example 5 wt % to 20 wt % based on a total amount the photosensitiveresin composition. When the binder resin is included within the aboverange, developability may be improved and excellent surface smoothnessmay be improved due to improved cross-linking during the manufacture ofa color filter.

(C) Photopolymerizable Monomer

The photopolymerizable monomer may be a mono-functional ormulti-functional ester of (meth)acrylic acid including at least oneethylenic unsaturated double bond.

The photopolymerizable monomer may cause sufficient polymerizationduring exposure in a pattern-forming process and form a pattern havingexcellent heat resistance, light resistance, and chemical resistance dueto the ethylenic unsaturated double bond.

Specific examples of the photopolymerizable monomer may be ethyleneglycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentylglycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritoldi(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, pentaerythritol hexa(meth)acrylate,dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate,dipentaerythritol penta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycolmonomethyl ether (meth)acrylate, trimethylol propane tri(meth)acrylate,tris(meth)acryloyloxyethyl phosphate, novolacepoxy (meth)acrylate, andthe like.

Commercially available examples of the photopolymerizable monomer may beas follows. The mono-functional (meth)acrylic acid ester may includeAronix M-101®, M-111®, M-114® (Toagosei Chemistry Industry Co., Ltd.);KAYARAD TC-110S®, TC-120S® (Nippon Kayaku Co., Ltd.); V-158®, V-2311®(Osaka Organic Chemical Ind., Ltd.), and the like. Examples of adifunctional (meth)acrylic acid ester may include Aronix M-210®, M-240®,M-6200® (Toagosei Chemistry Industry Co., Ltd.), KAYARAD HDDA®, HX-220®,R-604® (Nippon Kayaku Co., Ltd.), V-260®, V-312®, V-335 HP® (OsakaOrganic Chemical Ind., Ltd.), and the like. Examples of a tri-functional(meth)acrylic acid ester may include Aronix M-309®, M-400®, M-405®,M-450®, M-7100®, M-8030®, M-8060® (Toagosei Chemistry Industry Co.,Ltd.); KAYARAD TMPTA®, DPCA-20®, DPCA-30®, DPCA-60®, DPCA-120® (NipponKayaku Co., Ltd.); V-295®, V-300®, V-360®, V-GPT®, V-3PA®, V-400® (OsakaYuki Kayaku Kogyo Co. Ltd.), and the like. These may be used alone or asa mixture of two or more.

The photopolymerizable monomer may be treated with acid anhydride toimprove developability.

The photopolymerizable monomer may be included in an amount of 0.1 wt %to 30 wt %, for example 5 wt % to 20 wt % based on a total amount of thephotosensitive resin composition. When the photopolymerizable monomer isincluded within the range, pattern characteristic and developabilityduring manufacture of a color filter may be improved.

(D) Photopolymerization Initiator

The photopolymerization initiator may be an acetophenone-based compound,a benzophenone-based compound, a thioxanthone-based compound, abenzoin-based compound, a triazine-based compound, an oxime-basedcompound, and the like.

Examples of the acetophenone-based compound may be 2,2′-diethoxyacetophenone, 2,2′-dibutoxy acetophenone,2-hydroxy-2-methylpropinophenone, p-t-butyltrichloro acetophenone,p-t-butyldichloro acetophenone, 4-chloro acetophenone,2,2′-dichloro-4-phenoxy acetophenone,2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and thelike.

Examples of the benzophenone-based compound may be benzophenone, benzoylbenzoate, benzoyl methyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone,4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone,4,4′-dimethylaminobenzophenone, 4,4′-dichlorobenzophenone,3,3′-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound may be thioxanthone,2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone,2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, and the like.

Examples of the benzoin-based compound may be benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutylether, benzyldimethylketal, and the like.

Examples of the triazine-based compound may be2,4,6-trichloro-s-triazine, 2-phenyl4,6-bis(trichloromethyl)-s-triazine,2-(3′,4′-dimethoxystyryI)-4,6-bis(trichloromethyl)-s-triazine,2-(4′-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl4,6-bis(trichloromethyl)-s-triazine,bis(trichloromethyl)-6-styryl-s-triazine,2-(naphthol-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-methoxynaphthol-yl)-4,6-bis(trichloromethyl)-s-triazine,2-4-trichloromethyl(piperonyl)-6-triazine, 2-4-trichloromethyl(4′-methoxystyryl)-6-triazine, and the like.

Examples of the oxime-based compound may be2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione,1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone,and the like.

The photopolymerization initiator may further include a carbazole-basedcompound, a diketone-based compound, a sulfonium borate-based compound,a diazo-based compound, an imidazole-based compound, a biimidazole-basedcompound, a fluorene-based compound, and the like in addition to thecompounds.

The photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt %, for example 1 wt % to 3 wt % based on a total amount of thephotosensitive resin composition. When the photopolymerization initiatoris included within the range, the composition may be sufficientlyphotopolymerized when exposed to light during the pattern-formingprocess for preparing a color filter, accomplishing excellentsensitivity and improving transmittance.

(E) Solvent

The solvent is not particularly limited and specifically for example,alcohols such as methanol, ethanol, and the like; ethers such asdichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether,tetrahydrofuran, and the like; glycol ethers such as ethylene glycolmethyl ether, ethylene glycol ethyl ether, propylene glycol methyl etherand the like; shellosolve acetates such as methyl shellosolve acetate,ethyl shellosolve acetate, diethyl shellosolve acetate, and the like;carbitols such as methylethyl carbitol, diethyl carbitol, diethyleneglycol monomethyl ether, diethylene glycol monoethyl ether, diethyleneglycol dimethyl ether, diethylene glycol methylethyl ether, diethyleneglycol diethyl ether, and the like; propylene glycol alkyl etheracetates such as propylene glycol methyl ether acetate, propylene glycolpropyl ether acetate, and the like; aromatic hydrocarbons such astoluene, xylene, and the like; ketones such as methylethylketone,cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propylketone,methyl-n-butylketone, methyl-n-amylketone, 2-heptanone and the like;saturated aliphatic monocarboxylic acid alkyl esters such as ethylacetate, n-butyl acetate, isobutyl acetate, and the like; lactic acidalkyl esters such as methyl lactate, ethyl lactate, and the like;hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethylhydroxyacetate, butyl hydroxyacetate, and the like; acetic acidalkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate,methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, and thelike; 3-hydroxypropionic acid alkyl esters such as methyl3-hydroxypropionate, ethyl 3-hydroxypropionate, and the like;3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate,ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl3-ethoxypropionate, and the like; 2-hydroxypropionic acid alkyl esterssuch as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl2-hydroxypropionate, and the like; 2-alkoxypropionic acid alkyl esterssuch as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl2-ethoxypropionate, methyl 2-ethoxypropionate, and the like;2-hydroxy-2-methylpropionic acid alkyl esters such as methyl2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, andthe like; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and thelike; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethylpropionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate,and the like; or ketonate esters such as ethyl pyruvate, and the like,and additionally N-methylformamide, N,N-dimethyl formamide,N-methylformanilide, N-methylacetamide, N,N-dimethyl acetamide,N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexylether, acetylacetone, isophorone, caproic acid, caprylic acid,1-octanol, 1-nonanol, benzylalcohol, benzyl acetate, ethyl benzoate,diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate,propylene carbonate, phenyl shellosolve acetate, and the like, which maybe used alone or as a mixture of two or more.

Considering miscibility and reactivity, the solvent may desirably beglycol ethers such as ethylene glycol monoethyl ether, and the like;ethylene glycol alkyl ether acetates such as ethyl shellosolve acetate,and the like; esters such as 2-hydroxyethyl propionate, and the like;diethylene glycols such as diethylene glycol monomethyl ether, and thelike; propylene glycol alkylether acetates such as propylene glycolmonomethyl ether acetate, propylene glycol propyl ether acetate, and thelike.

The solvent is used in a balance amount, and specifically 20 wt % to 90wt % based on a total amount of the photosensitive resin composition.The photosensitive resin composition for a color filter has a coatingproperty, and may maintain excellent flatness of a film having athickness of 3 μm or greater.

(F) Other Additives

The photosensitive resin composition may further include an additivesuch as malonic acid; 3-amino-1,2-propanediol; a silane-based couplingagent including a vinyl group or a (meth)acryloxy group; a levelingagent; a fluorine-based surfactant; a radical polymerization initiator,and the like in order to prevent stains or spots during the coating, toadjust leveling, or to prevent pattern residue due to non-development.

In addition, the photosensitive resin composition may further include anadditive such as an epoxy compound, and the like in order to improve aclose contacting property with a substrate.

Examples of the epoxy compound may be a phenol novolac epoxy compound, atetramethyl biphenyl epoxy compound, a bisphenol A epoxy compound, analicyclic epoxy compound, or a combination thereof.

An amount of the additive may be controlled according to desirableproperties.

Another embodiment provides a color filter manufactured using thephotosensitive resin composition is provided. A method of manufacturingthe color filter is as follows.

The photosensitive resin composition for a color filter is coated on abare glass substrate, or on a glass substrate on which SiN_(x) is coatedin a thickness of 500 Å to 1500 Å as a protective layer using anappropriate method of spin-coating, slit-coating, and the like to have athickness of 3.1 μm to 3.4 μm. After the coating, light is irradiated toform a pattern required for a color filter. After irradiation, thecoated layer is treated with an alkali developing solution, and anon-radiated region of the coated layer may be dissolved, forming apattern for an image color filter. This process is repeated depending onthe necessary number of R, G, and B colors, fabricating a color filterhaving a desired pattern.

In addition, the image pattern acquired by the development is curedthrough heat treatment, actinic ray radiation, or the like, resultantlyimproving crack resistance, solvent resistance, and the like.

Hereinafter, the present invention is preferably in more detail withreference to examples. These examples, however, are not in any sense tobe interpreted as limiting the scope of the invention.

Intermediate Synthesis Example 1 Synthesis of Intermediate A

2,4-dimethyldiphenylamine (10 mol), benzyl bromide (10 mol), and sodiumhydride (10 mol) were put in N,N-dimethyl formamide, and the mixture washeated up to 80° C. and stirred for 24 hours. Ethyl acetate was added tothe solution, and the obtained mixture is twice washed to extract anorganic layer. The extracted organic layer was distilled under a reducedpressure and separated through column chromatography to obtainIntermediate A.

Intermediate Synthesis Example 2 Synthesis of Intermediate B

2,4-dimethyldiphenylamine (10 mol), (1-bromoethyl)benzene (10 mol), andsodium hydride (10 mol) were put in N,N-dimethyl formamide, and themixture was heated up to 80° C. and stirred for 24 hours. Ethyl acetatewas added thereto, and the obtained mixture was twice washed to extractan organic layer. The extracted organic layer was distilled under areduced pressure and separated through column chromatography to obtainIntermediate B.

Intermediate Synthesis Example 3 Synthesis of Intermediate C

2,4-dimethyldiphenylamine (10 mol), a-bromo-p-xylene (10 mol), andsodium hydride (10 mol) were put in N,N-dimethyl formamide, and themixture was heated up to 80° C. and stirred for 24 hours. Ethyl acetatewas added thereto, and the obtained mixture was twice washed to extractan organic layer. The extracted organic layer was distilled under areduced pressure and separated through column chromatography to obtainIntermediate C.

Intermediate Synthesis Example 4 Synthesis of Intermediate D

2,4-dimethyldiphenylamine (10 mol), a-bromo-o-xylene (10 mol), andsodium hydride (10 mol) were put in N,N-dimethyl formamide, and themixture was heated up to 80° C. and stirred for 24 hours. Ethyl acetatewas added thereto, and the obtained mixture was twice washed to extractan organic layer. The extracted organic layer was distilled under areduced pressure and separated through column chromatography to obtainIntermediate D.

Intermediate Synthesis Example 5 Synthesis of Intermediate E

2,4-dimethyldiphenylamine (10 mol), a-bromo-m-xylene (10 mol), andsodium hydride (10 mol) were put in N,N-dimethyl formamide, and theobtained mixture was heated up to 80° C. and stirred for 24 hours. Ethylacetate was added thereto, and the obtained mixture was twice washed toextract an organic layer. The extracted organic layer was distilledunder a reduced pressure and separated through column chromatography toobtain Intermediate E.

Intermediate Synthesis Example 6 Synthesis of Intermediate F

2,4-dimethyldiphenylamine (10 mol), 2,4-dimethylbenzyl chloride (10mol), and sodium hydride (10 mol) were put in N,N-dimethyl formamide,and the mixture was heated up to 80° C. and stirred for 24 hours. Ethylacetate was added thereto, and the obtained mixture was twice washed toextract an organic layer. The extracted organic layer was distilledunder a reduced pressure and separated through column chromatography toobtain Intermediate F.

Intermediate Synthesis Example 7 Synthesis of Intermediate G

2,4-dimethyldiphenylamine (10 mol), 2,4-dimethylbenzyl chloride (10mol), and sodium hydride (10 mol) were put in N,N-dimethyl formamide,and the mixture was heated up to 80° C. and stirred for 24 hours. Ethylacetate was added thereto, and the obtained mixture was twice washed toextract an organic layer. The extracted organic layer was distilledunder a reduced pressure and separated through column chromatography toobtain Intermediate G.

Synthesis Example 1 Synthesis of Compound Represented by ChemicalFormula 1-1

Intermediate A (60 mmol) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (30mmol) were added to toluene (200 mL) and butanol (200 mL), and watergenerated by refluxing the obtained mixture was removed with aDean-stark distillator. After stirred for 12 hours, a green producttherefrom was distilled under a reduced pressure and purified throughcolumn chromatography to synthesize a compound represented by ChemicalFormula 1-1.

Synthesis Example 2 Synthesis of Compound Represented by ChemicalFormula 1-2

Intermediate B (60 mmol) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (30mmol) were added to toluene (200 mL) and butanol (200 mL), and watergenerated by refluxing the mixture was removed with a Dean-starkdistillator. After stirred for 12 hours, a green product therefrom wasdistilled under a reduced pressure and purified through columnchromatography to synthesize a compound represented by Chemical Formula1-2.

Synthesis Example 3 Synthesis of Compound Represented by ChemicalFormula 1-3

Intermediate C (60 mmol) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (30mmol) were added to toluene (200 mL) and butanol (200 mL), and watergenerated by refluxing the mixture was removed with a Dean-starkdistillator. After stirred for 12 hours, a green product therefrom wasdistilled under a reduced pressure and purified through columnchromatography to synthesize a compound represented by Chemical Formula1-3.

Synthesis Example 4 Synthesis of Compound Represented by ChemicalFormula 1-4

Intermediate D (60 mmol) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (30mmol) were added to toluene (200 mL) and butanol (200 mL), and watergenerated by refluxing the mixture was removed with a Dean-starkdistillator. After stirred for 12 hours, a green product therefrom wasdistilled under a reduced pressure and purified through columnchromatography to synthesize a compound represented by Chemical Formula1-4.

Synthesis Example 5 Synthesis of Compound Represented by ChemicalFormula 1-5

Intermediate E (60 mmol) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (30mmol) were added to toluene (200 mL) and butanol (200 mL), and watergenerated by refluxing the mixture was removed with a Dean-starkdistillator. After stirred for 12 hours, a green product therefrom wasdistilled under a reduced pressure and purified through columnchromatography to synthesize a compound represented by Chemical Formula1-5.

Synthesis Example 6 Synthesis of Compound Represented by ChemicalFormula 1-6

Intermediate F (60 mmol) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (30mmol) were added to toluene (200 mL) and butanol (200 mL), and watergenerated by refluxing the mixture was removed with a Dean-starkdistillator. After stirred for 12 hours, a green product therefrom wasdistilled under a reduced pressure and purified through columnchromatography to obtain a compound represented by Chemical Formula 1-6.

Synthesis Example 7 Synthesis of Compound Represented by ChemicalFormula 1-7

Intermediate G (60 mmol) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (30mmol) were added to toluene (200 mL) and butanol (200 mL), and watergenerated by refluxing the mixture was removed with a Dean-starkdistillator. After stirred for 12 hours, a green product therefrom wasdistilled under a reduced pressure and purified through columnchromatography to synthesize a compound represented by Chemical Formula1-7.

Synthesis Example 8 Synthesis of Core-Shell Dye Represented by ChemicalFormula 6

The compound represented by Chemical Formula 1-1 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and a solution obtained by dissolvingisophthaloyl chloride (20 mmol) and p-xylylene diamine (20 mmol) in 60mL of chloroform was added in a dropwise fashion thereto at roomtemperature for 5 hours. After 12 hours, the obtained mixture wasdistilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 6.

Synthesis Example 9 Synthesis of Core-Shell Dye Represented by ChemicalFormula 7

The compound represented by Chemical Formula 1-1 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and triethylamine (50 mmol) was addedthereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and theobtained solution was added in a dropwise fashion to the above solutionat room temperature for 5 hours. After 12 hours, the obtained mixturewas distilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 7.

Synthesis Example 10 Synthesis of Core-Shell Dye Represented by ChemicalFormula 8

The compound represented by Chemical Formula 1-2 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and a solution obtained by dissolvingisophthaloyl chloride (20 mmol) and p-xylylene diamine (20 mmol) in 60mL of chloroform was added in a dropwise fashion thereto at roomtemperature for 5 hours. After 12 hours, the obtained mixture wasdistilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 8.

Synthesis Example 11 Synthesis of Core-Shell Dye Represented by ChemicalFormula 9

The compound represented by Chemical Formula 1-2 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and triethylamine (50 mmol) was addedthereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and theobtained solution was added to the above solution at room temperaturefor 5 hours. After 12 hours, the obtained mixture was distilled under areduced pressure and separated through column chromatography tosynthesize a core-shell dye represented by Chemical Formula 9.

Synthesis Example 12 Synthesis of Core-Shell Dye Represented by ChemicalFormula 10

The compound represented by Chemical Formula 1-3 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and a solution obtained by dissolvingisophthaloyl chloride (20 mmol) and p-xylylene diamine (20 mmol) in 60mL of chloroform was added thereto in a dropwise fashion at roomtemperature for 5 hours. After 12 hours, the obtained mixture wasdistilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 10.

Synthesis Example 13 Synthesis of Core-Shell Dye Represented by ChemicalFormula 11

The compound represented by Chemical Formula 1-3 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and triethylamine (50 mmol) was addedthereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and theobtained solution was added to the above solution in a dropwise fashionat room temperature for 5 hours. After 12 hours, the obtained mixturewas distilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 11.

Synthesis Example 14 Synthesis of Core-Shell Dye Represented by ChemicalFormula 12

The compound represented by Chemical Formula 1-4 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and a solution obtained by dissolvingisophthaloyl chloride (20 mmol) and p-xylylene diamine (20 mmol) in 60mL of chloroform was added in a dropwise fashion thereto at roomtemperature for 5 hours. After 12 hours, the obtained mixture wasdistilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 12.

Synthesis Example 15 Synthesis of Core-Shell Dye Represented by ChemicalFormula 13

The compound represented by Chemical Formula 1-4 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and triethylamine (50 mmol) was addedthereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and theobtained solution was added in a dropwise fashion to the above solutionat room temperature for 5 hours. After 12 hours, the obtained mixturewas distilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 13.

Synthesis Example 16 Synthesis of Core-Shell Dye Represented by ChemicalFormula 14

The compound represented by Chemical Formula 1-5 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and a solution obtained by dissolvingisophthaloyl chloride (20 mmol) and p-xylylene diamine (20 mmol) in 60mL of chloroform was added thereto in a dropwise fashion at roomtemperature for 5 hours. After 12 hours, the obtained mixture wasdistilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 14.

Synthesis Example 17 Synthesis of Core-Shell Dye Represented by ChemicalFormula 15

The compound represented by Chemical Formula 1-5 (5 mmol) is dissolvedin 600 mL of a chloroform solvent, and triethylamine (50 mmol) is addedthereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and theobtained solution was added to the above solution in a dropwise fashionat room temperature for 5 hours. After 12 hours, the obtained mixturewas distilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 15.

Synthesis Example 18 Synthesis of Core-Shell Dye Represented by ChemicalFormula 16

The compound represented by Chemical Formula 1-6 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and a solution obtained by dissolvingisophthaloyl chloride (20 mmol) and p-xylylene diamine (20 mmol) in 60mL of chloroform was added thereto in a dropwise fashion at roomtemperature for 5 hours. After 12 hours, the obtained mixture wasdistilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 16.

Synthesis Example 19 Synthesis of Core-Shell Dye Represented by ChemicalFormula 17

The compound represented by Chemical Formula 1-6 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and triethylamine (50 mmol) was addedthereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and theobtained solution was added in a dropwise fashion to the above solutionat room temperature for 5 hours. After 12 hours, the obtained mixturewas distilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 17.

Synthesis Example 20 Synthesis of Core-Shell Dye Represented by ChemicalFormula 18

The compound represented by Chemical Formula 1-7 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and a solution obtained by dissolvingisophthaloyl chloride (20 mmol) and p-xylylene diamine (20 mmol) in 60mL of chloroform was added in a dropwise fashion thereto at roomtemperature for 5 hours. After 12 hours, the obtained mixture wasdistilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 18.

Synthesis Example 21 Synthesis of Core-Shell Dye Represented by ChemicalFormula 19

The compound represented by Chemical Formula 1-7 (5 mmol) was dissolvedin 600 mL of a chloroform solvent, and triethylamine (50 mmol) was addedthereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and theobtained solution was added to the above solution in a dropwise fashionat room temperature for 5 hours. After 12 hours, the obtained mixturewas distilled under a reduced pressure and separated through columnchromatography to synthesize a core-shell dye represented by ChemicalFormula 19.

Comparative Synthesis Example 1 Synthesis of Core-Shell Dye

398 mg of squaric acid and 2.23 g of 2-(3-(dibutylamino)phenoxy)ethylacrylate were put in a 100 mL 3-necked flask, 40 mL of n-butanol and 20mL of toluene were added thereto, and the mixture was heated andrefluxed at 120° C. for 5 hours. Water produced during a reaction wasremoved by using a Dean-Stark trap set, and the reaction was promoted.When the reaction was complete, a resultant therefrom was cooled downand then, extracted with methylene chloride and treated through columnchromatography to synthesize a compound represented by Chemical FormulaX at a yield of 60%. Subsequently, 0.72 g (1 mmol) of the compoundrepresented by Chemical Formula X and 2.02 g (1 mmol) of triacetylβ-cyclodextrin represented by Chemical Formula Y (CAS #23739-88-0, TCI)were dissolved in 50 ml of dichloromethane, and the solution was stirredfor about 12 hours at room temperature and then, after completelyremoving the solvent under a reduced pressure, dried to obtain about 2.7g of a core-shell dye in a solid state. The core-shell dye had astructure that the compound represented by Chemical Formula Y surroundedthe compound represented by Chemical Formula X.

Comparative Synthesis Example 2 Synthesis of Compound Represented byChemical Formula Z

398 mg of squaric acid and 2.23 g of2-(3-(methyl(phenyl)amino)propylamino)ethyl acrylate were put in a 100mL 3-necked flask, 40 mL of n-butanol and 20 mL of toluene were addedthereto, and the obtained mixture was heated and refluxed at 120° C. for5 hours. Water produced during a reaction was removed by using aDean-Stark trap set, and the reaction was promoted. When the reactionwas complete, a resultant therefrom was cooled down and then, extractedwith methylene chloride and treated through column chromatography toobtain a compound represented by Chemical Formula Z at a yield of 60%.

Maldi-tof MS: 514.26 m/z

Comparative Synthesis Example 3 Synthesis of Compound Represented byChemical Formula 101

(2,4-Dimethyl-phenyl)-(2-ethyl-hexyl)-phenyl-amine (60 mmol) and3,4-dihydroxy-3-cyclobutene-1,2-dione (30 mmol) were added to toluene(200 mL) and butanol (200 mL), and water generated by refluxing themixture was removed with a Dean-stark distillator. After 12 hours, agreen product therefrom was distilled under a reduced pressure andpurified through column chromatography to synthesize a compoundrepresented by Chemical Formula 101.

Maldi-tof MS: 697.02 m/z

Comparative Synthesis Example 4 Synthesis of Compound Represented byChemical Formula 102

Benzyl-isopropyl-phenyl-amine (60 mmol) and3,4-dihydroxy-3-cyclobutene-1,2-dione (30 mmol) were added to toluene(200 mL) and butanol (200 mL), and water generated by refluxing themixture was removed with a Dean-stark distillator. After stirred for 12hours, a green reactant therefrom was distilled under a reduced pressureand purified through column chromatography to synthesize a compoundrepresented by Chemical Formula 102.

Maldi-tof MS: 528.70 m/z

Comparative Synthesis Example 5 Synthesis of Compound Represented byChemical Formula 103

Diisopropyl-phenyl-amine (60 mmol) and3,4-dihydroxy-3-cyclobutene-1,2-dione (30 mmol) were added to toluene(200 mL) and butanol (200 mL), and water generated by refluxing themixture was removed with a Dean-stark distillator. After stirred for 12hours, a green product therefrom was distilled under a reduced pressureand purified through column chromatography to synthesize a compoundrepresented by Chemical Formula 103.

Maldi-tof MS: 432.61 m/z

Comparative Synthesis Example 6 Synthesis of Compound Represented byChemical Formula 104

Bis-(2,4-dimethyl-phenyl)-phenyl-amine (60 mmol) and3,4-dihydroxy-3-cyclobutene-1,2-dione (30 mmol) were added to toluene(200 mL) and butanol (200 mL), and water produced by refluxing themixture was removed with a Dean-stark distillator. After stirred for 12hours, a green product therefrom was distilled under a reduced pressureand purified through column chromatography to synthesize a compoundrepresented by Chemical Formula 104.

Maldi-tof MS: 680.89 m/z

(Preparation of Photosensitive Resin Composition)

Photosensitive resin compositions were prepared using the followingcomponents.

(A) Dye

(A-1) Compound prepared in Synthesis Example 1 (represented by ChemicalFormula 1-1)

(A-2) Compound prepared in Synthesis Example 2 (represented by ChemicalFormula 1-2)

(A-3) Compound prepared in Synthesis Example 3 (represented by ChemicalFormula 1-3)

(A-4) Compound prepared in Synthesis Example 4 (represented by ChemicalFormula 1-4)

(A-5) Compound prepared in Synthesis Example 5 (represented by ChemicalFormula 1-5)

(A-6) Compound prepared in Synthesis Example 6 (represented by ChemicalFormula 1-6)

(A-7) Compound prepared in Synthesis Example 7 (represented by ChemicalFormula 1-7)

(A-8) Core-shell dye prepared in Synthesis Example 8 (represented byChemical Formula 6)

(A-9) Core-shell dye prepared in Synthesis Example 9 (represented byChemical Formula 7)

(A-10) Core-shell dye prepared in Synthesis Example 10 (represented byChemical Formula 8)

(A-11) Core-shell dye prepared in Synthesis Example 11 (represented byChemical Formula 9)

(A-12) Core-shell dye prepared in Synthesis Example 12 (represented byChemical Formula 10)

(A-13) Core-shell dye prepared in Synthesis Example 13 (represented byChemical Formula 11)

(A-14) Core-shell dye prepared in Synthesis Example 14 (represented byChemical Formula 12)

(A-15) Core-shell dye prepared in Synthesis Example 15 (represented byChemical Formula 13)

(A-16) Core-shell dye prepared in Synthesis Example 16 (represented byChemical Formula 14)

(A-17) Core-shell dye prepared in Synthesis Example 17 (represented byChemical Formula 15)

(A-18) Core-shell dye prepared in Synthesis Example 18 (represented byChemical Formula 16)

(A-19) Core-shell dye prepared in Synthesis Example 19 (represented byChemical Formula 17)

(A-20) Core-shell dye prepared in Synthesis Example 20 (represented byChemical Formula 18)

(A-21) Core-shell dye prepared in Synthesis Example 21 (represented byChemical Formula 19)

(A-22) Core-shell dye prepared in Comparative Synthesis Example 1

(A-23) Compound prepared in Comparative Synthesis Example 2 (representedby Chemical Formula Z)

(A-24) Compound prepared in Comparative Synthesis Example 3 (representedby Chemical Formula 101)

(A-25) Compound prepared in Comparative Synthesis Example 4 (representedby Chemical Formula 102)

(A-26) Compound prepared in Comparative Synthesis Example 5 (representedby Chemical Formula 103)

(A-27) Compound prepared in Comparative Synthesis Example 6 (representedby Chemical Formula 104)

(A′) Pigment Dispersion Liquid

(A′-1) C.I. green pigment 7

(A′-2) C.I. green pigment 36

(B) Binder Resin

A methacrylic acid/benzyl methacrylate copolymer having a weight averagemolecular weight of 22,000 g/mol (a mixing weight ratio: 15 wt %/85 wt%)

(C) Photopolymerizable Monomer

Dipentaerythritol hexaacrylate

((D) Photopolymerization Initiator

(D-1) 1,2-octandione

(D-2)2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one

(E) Solvent

(E-1) Cyclohexanone

(E-2) Propylene glycol monomethyl ether acetate

Example 1 to Example 21 and Comparative Examples 1 to ComparativeExample 8

Photosensitive resin compositions were prepared by mixing each componentin the compositions shown in Table 1 to Table 4. Specifically, aphotopolymerization initiator was dissolved in a solvent, the solutionwas stirred at room temperature for 2 hours, a dye (or pigmentdispersion liquid) was added thereto, the mixture was stirred for 30minutes, a binder resin and a photopolymerizable monomer were addedthereto, and the obtained mixture was stirred at room temperature for 2hours. The solution was three times filtered to remove impurities andprepare a photosensitive resin composition.

TABLE 1 (unit: wt %) Examples 1 2 3 4 5 6 7 8 9 (A) A-1 2 — — — — — — —— Dye A-2 — 2 — — — — — — — A-3 — — 2 — — — — — — A-4 — — — 2 — — — — —A-5 — — — — 2 — — — — A-6 — — — — — 2 — — — A-7 — — — — — — 2 — — A-8 —— — — — — — 2 — A-9 — — — — — — — — 2 (A′) A′-1 — — — — — — — — —Pigment A′-2 — — — — — — — — — dispersion liquid (B) Binder resin 3.53.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) 8 8 8 8 8 8 8 8 8 Photopolymerizablemonomer (D) D-1 1 1 1 1 1 1 1 1 1 Photo D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.50.5 0.5 polymerization initiator (E) E-1 40 40 40 40 40 40 40 40 40Solvent E-2 45 45 45 45 45 45 45 45 45 Total 100 100 100 100 100 100 100100 100

TABLE 2 (unit: wt %) Examples 10 11 12 13 14 15 16 17 18 (A) A-10 2 — —— — — — — — Dye A-11 — 2 — — — — — — — A-12 — — 2 — — — — — — A-13 — — —2 — — — — — A-14 — — — — 2 — — — — A-15 — — — — — 2 — — — A-16 — — — — —— 2 — — A-17 — — — — — — — 2 — A-18 — — — — — — — — 2 (A′) A′-1 — — — —— — — — — Pigment A′-2 — — — — — — — — — dispersion liquid (B) Binderresin 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) 8 8 8 8 8 8 8 8 8Photopolymerizable monomer (D) D-1 1 1 1 1 1 1 1 1 1 Photo D-2 0.5 0.50.5 0.5 0.5 0.5 0.5 0.5 0.5 polymerization initiator (E) E-1 40 40 40 4040 40 40 40 40 Solvent E-2 45 45 45 45 45 45 45 45 45 Total 100 100 100100 100 100 100 100 100

TABLE 3 (unit: wt %) Examples Comparative Examples 19 20 21 1 2 3 4 5 6(A) A-19 2 — — — — — — — — Dye A-20 — 2 — — — — — — — A-21 — — 2 — — — —— — A-22 — — — 2 — — — — — A-23 — — — — 2 — — — — A-24 — — — — — 2 — — —A-25 — — — — — — 2 — — A-26 — — — — — — — 2 — A-27 — — — — — — — — 2(A′) A′-1 — — — — — — — — — Pigment A′-2 — — — — — — — — — dispersionliquid (B) Binder resin 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) 8 8 8 88 8 8 8 8 Photopolymerizable monomer (D) D-1 1 1 1 1 1 1 1 1 1 Photo D-20.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 polymerization initiator (E) E-1 4040 40 40 40 40 40 40 40 Solvent E-2 45 45 45 45 45 45 45 45 45 Total 100100 100 100 100 100 100 100 100

TABLE 4 (unit: wt %) Comparative Examples 7 8 (A′) Pigment A′-1 35 —dispersion liquid A′-2 — 35 (B) Binder resin 2.5 2.5 (C)Photopolymerizable monomer 5 5 (D) D-1 1 1 Photopolymerization D-2 0.50.5 initiator (E) Solvent E-1 40 40 E-2 16 16 Total 100 100(Evaluation)Evaluation 1: Luminance and Contrast Ratio

The photosensitive resin compositions according to Example 1 to Example21 and Comparative Example 1 to Comparative Example 8 were respectivelycoated to be 1 μm to 3 μm thick on a 1 mm-thick degreased glasssubstrate and dried on a 90° C. hot plate for 2 minutes to obtain films.Subsequently, the films were exposed to light with a high pressuremercury lamp having a main wavelength of 365 nm and dried in forcedconvection drying furnace of a 200° C. oven for 5 minutes. Luminance andcontrast ratios of pixel layers were measured using a spectrophotometer(MCPD3000, Otsuka electronic Co., Ltd.) and the results are shown inTable 5.

TABLE 5 Luminance Contrast ratio Example 1 65.2 14200 Example 2 65.314540 Example 3 65.0 14200 Example 4 65.5 14300 Example 5 65.5 14200Example 6 65.3 14600 Example 7 65.0 14500 Example 8 67.1 14400 Example 967.9 14800 Example 10 67.2 14400 Example 11 67.9 14900 Example 12 67.414400 Example 13 67.7 14700 Example 14 67.3 13900 Example 15 67.6 14700Example 16 67.4 13900 Example 17 67.7 14800 Example 18 67.2 14400Example 19 67.7 14200 Example 20 67.3 14200 Example 21 67.7 14900Comparative Example 1 64.0 12800 Comparative Example 2 64.1 13700Comparative Example 3 64.5 13200 Comparative Example 4 64.4 12900Comparative Example 5 64.2 13700 Comparative Example 6 64.3 13800Comparative Example 7 62.4 12100 Comparative Example 8 63.1 12300

Referring to Table 5, Example 1 to Example 21 including a monomoleculardye or a core-shell dye according to one embodiment of the presentinvention showed high luminance and a high contrast ratio compared withComparative Example 1 to Comparative Example 8 including neither themonomolecular dye nor the core-shell dye.

Evaluation 2: Durability

The photosensitive resin compositions according to Example 8 to Example21 and Comparative Example 1 to Comparative Example 8 were respectivelycoated to be 1 μm to 3 μm thick on a 1 mm-thick degreased glasssubstrate and dried on a 90° C. hot plate for 2 minutes to obtain films.The films were exposed to light with a high pressure mercury lamp havinga main wavelength of 365 nm and dried in a 200° C. oven for 20 minutes,and a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.) tomeasure color coordinate changes and thus evaluate durability, and theresults are shown in Table 6.

Evaluation Reference of Durability

◯: color coordinate change of less than or equal to 0.003

Δ: color coordinate change of greater than 0.003 and less than or equalto 0.005

X: color coordinate change of greater than 0.005

TABLE 6 Durability Example 8 ◯ Example 9 ◯ Example 10 ◯ Example 11 ◯Example 12 ◯ Example 13 ◯ Example 14 ◯ Example 15 ◯ Example 16 ◯ Example17 ◯ Example 18 ◯ Example 19 ◯ Example 20 ◯ Example 21 ◯ ComparativeExample 1 X Comparative Example 2 X Comparative Example 3 Δ ComparativeExample 4 Δ Comparative Example 5 Δ Comparative Example 6 X ComparativeExample 7 X Comparative Example 8 X

Referring to Table 6, Example 8 to Example 21 including the core-shelldye according to an embodiment showed excellent durability compared withComparative Example 1 to Comparative Example 8 without the core-shelldye.

While this invention has been described in connection with what ispresently considered to be practical example embodiments, it is to beunderstood that the invention is not limited to the disclosedembodiments, but, on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims. Therefore, the aforementioned embodimentsshould be understood to be exemplary but not limiting the presentinvention in any way.

What is claimed is:
 1. A compound represented by Chemical Formula 1:

wherein, in Chemical Formula 1, R¹ is a group represented by ChemicalFormula 2, and R² is a group represented by Chemical Formula 3,

wherein, in Chemical Formula 2, R³ is a hydrogen atom or a substitutedor unsubstituted C1 to C10 alkyl group, R⁴ is a substituted orunsubstituted C1 to C10 alkyl group, and n is an integer ranging from 0to 5,

wherein in Chemical Formula 3, R⁵ and R⁶ are independently a C1 to C7alkyl group.
 2. The compound of claim 1, wherein the n is an integer of1 or
 2. 3. The compound of claim 1, wherein the compound represented byChemical Formula 1 is represented by one selected from compoundsrepresented by Chemical Formula 1-1 to Chemical Formula 1-7:


4. A core-shell dye comprising a core including the compound of claim 1;and a shell surrounding the core.
 5. The core-shell dye of claim 4,wherein the shell is represented by Chemical Formula 4 or ChemicalFormula 5:

wherein in, Chemical Formula 4 and Chemical Formula 5, La to Ld areindependently a single bond or a substituted or unsubstituted C1 to C10alkylene group.
 6. The core-shell dye of claim 5, wherein La to Ld areindependently a substituted or unsubstituted C1 to C10 alkylene group.7. The core-shell dye of claim 4, wherein the shell is represented byChemical Formula 4-1 or Chemical Formula 5-1:


8. The core-shell dye of claim 7, wherein the shell has a cage width of6.5 Å to 7.5 Å.
 9. The core-shell dye of claim 4, wherein the core has alength of 1 nm to 3 nm.
 10. The core-shell dye of claim 4, wherein thecore has a maximum absorption peak in a wavelength of 530 nm to 680 nm.11. The core-shell dye of claim 4, wherein the core-shell dye isselected from compounds represented by Chemical Formula 6 to ChemicalFormula 19:


12. The core-shell dye of claim 4, wherein the core-shell dye includesthe core and the shell in a mole ratio of 1.1.
 13. The core-shell dye ofclaim 4, wherein the core-shell dye is a green dye.
 14. A photosensitiveresin composition comprising the compound of claim
 1. 15. Thephotosensitive resin composition of claim 14, wherein the photosensitiveresin composition further includes a binder resin, a photopolymerizablemonomer, a photopolymerization initiator, and a solvent.
 16. Thephotosensitive resin composition of claim 15, wherein the photosensitiveresin composition further includes a pigment.
 17. The photosensitiveresin composition of claim 15, wherein the photosensitive resincomposition includes 0.5 to 10 wt % of the compound; 0.1 to 30 wt % ofthe binder resin; 0.1 to 30 wt % of the photopolymerizable monomer; 0.1to 5 wt % of the photopolymerization initiator; and a balance amount ofthe solvent based on a total amount of the photosensitive resincomposition.
 18. The photosensitive resin composition of claim 15,wherein the photosensitive resin composition further includes malonicacid, 3-amino-1,2-propanediol, a silane-based coupling agent including avinyl group or a (meth)acryloxy group, a leveling agent, a surfactant, aradical polymerization initiator, or a combination thereof.
 19. A colorfilter manufactured using the photosensitive resin composition of claim14.